JP2012038534A - Positive electrode material for lithium secondary battery, lithium secondary battery and secondary battery module using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive electrode material for a lithium secondary battery, which can stably suppress heat generation, to provide a lithium secondary battery that uses the positive electrode material for a lithium secondary battery as a positive electrode material and is excellent in safety in a charged state, and to provide a secondary battery module using the lithium secondary battery.SOLUTION: A positive electrode material for a lithium secondary battery according to the present invention includes a coating layer on a surface of a lithium manganese composite oxide. The coating layer contains a phosphate compound and an oxide or fluoride containing A (A is one or more elements selected from the group consisting of Mg, Al, Ti and Cu). The lithium manganese composite oxide has a layered structure represented by the formula: LiMnMO(where, 0.1≤x≤0.6 and M is one or more elements selected from the group consisting of Li, Mg, Al, Ti, Co, Ni and Mo). In the coating layer, an atomic concentration of phosphorus on a surface layer side is higher than that of phosphorus on a side of the lithium manganese composite oxide.

Description

  The present invention relates to a lithium secondary battery.

Compared to other secondary batteries, lithium secondary batteries using lithium ions have a large ionization tendency of lithium, a small atomic weight, and high volume / weight energy density. Therefore, it is widely used as a power source for consumer equipment such as a mobile phone, a notebook personal computer, and a PDA (Personal Digital Assistant). Furthermore, in the future, it will be a power source for motor-driven electric vehicles driven by an environment where CO ₂ emissions are suppressed, a hybrid vehicle driven by a motor and an engine, and power storage of renewable energy such as solar power generation and wind power generation. It is expected to be deployed as large-scale applications such as power supplies for industrial use. In the field of such a large-sized lithium secondary battery, it is strongly required to have high safety and high capacity, in particular, as compared with a power supply for consumer equipment.

  Currently, lithium composite oxides having a layered structure such as lithium cobaltate and lithium nickelate are mainly used as positive electrode materials for lithium secondary batteries. However, these materials have unstable thermal stability in a charged state, and there is a problem in safety during abuse. In the case of a lithium composite oxide having a layered structure, when the temperature rises in the charged state, the crystal structure changes and oxygen is desorbed. This oxygen reacts with the electrolyte to cause an exothermic reaction. Therefore, in order to stabilize the crystal structure in a state where a part of lithium is removed by charging, a method of substituting a part of cobalt or nickel with a different element as in Patent Document 1 is general. However, when element substitution is small, the thermal stability cannot be sufficiently improved, and when element substitution is large, there is a problem that the capacity is reduced.

  The cause of the capacity decrease is a change in the valence of the transition metal in the positive electrode material due to element substitution. Therefore, in order to improve the thermal stability while maintaining the capacity, there is a method of coating the surface of the positive electrode material with a different compound. For example, in Patent Document 2, the surface of a lithium composite oxide having a layered structure is covered with an inorganic compound or a carbon material. Covering in this manner can suppress the oxidative decomposition of the electrolyte even at a high voltage, leading to an improvement in thermal stability. Moreover, in patent document 3, protrusion-like Al containing oxide and / or Al containing hydroxide are uniformly distributed on the positive electrode material surface, and in addition, the phosphoric acid compound is made to adhere. This suppresses decomposition of the non-aqueous electrolyte and elution of elements such as cobalt from the positive electrode material. In particular, the phosphoric acid compound has an effect of suppressing elution of the element from the positive electrode material. An example is described in which an acid compound is disposed in the vicinity of the positive electrode material and an Al compound is coated on the outside thereof.

Japanese Patent No. 3244314 JP-T-2004-319129 Special table 2009-245917

  In view of the role of a compound used for coating a lithium manganese composite oxide having a layered structure, an object of the present invention is to optimize the arrangement of the coating compound and improve the coating effect. Furthermore, it aims at providing the lithium secondary battery excellent in safety | security using the surface covering lithium manganese complex oxide excellent in thermal stability in a charged state as a positive electrode material.

  In order to achieve the above-mentioned target, the positive electrode material for a lithium secondary battery according to the first aspect of the present invention comprises a phosphoric acid compound and A (A is Mg, Al, Ti, Cu on the surface of the lithium manganese composite oxide). An oxide or fluoride containing at least one element selected from the group), and P in the phosphoric acid compound is a surface layer of the coating layer in the coating layer The atomic concentration on the side (electrolyte side) is higher than the atomic concentration on the lithium manganese composite oxide side.

  The lithium secondary battery according to the second aspect of the present invention includes the positive electrode material for a lithium secondary battery according to the first aspect of the present invention.

  A lithium secondary battery module according to a third aspect of the present invention includes a plurality of electrically connected lithium secondary batteries according to the second aspect of the present invention, and a voltage between terminals of the plurality of lithium secondary batteries, And a control device for controlling the states of the plurality of lithium secondary batteries.

  A lithium secondary battery module according to a fourth aspect of the present invention is a secondary battery module having a plurality of electrically connected batteries and a control device that manages and controls the state of the plurality of batteries, The control device detects a voltage between terminals of the plurality of batteries, and each of the plurality of batteries constitutes a laminated body having a positive electrode, a negative electrode, and an electrolyte in a battery can that constitutes the exterior thereof, and the positive electrode Is a lithium manganese composite oxide, and a phosphoric acid compound and A (A is one or more elements selected from the group consisting of Mg, Al, Ti, Cu) on the surface of the lithium manganese composite oxide In the coating layer, P in the phosphate compound has an atomic concentration on the surface layer side (electrolyte side) of the lithium manganese. Composite oxide side Higher than the atomic concentration.

  According to the present invention, a positive electrode material for a lithium secondary battery excellent in thermal stability even under a high voltage, and further, this lithium secondary battery positive electrode material is used as a positive electrode material, and the lithium secondary battery excellent in safety during charging is used. A secondary battery and a secondary battery module using the secondary battery can be realized.

It is the longitudinal cross-sectional schematic which shows the lithium secondary battery of embodiment which concerns on this invention. It is a figure which shows the X-ray-diffraction pattern of the positive electrode material of embodiment. It is a figure which shows distribution of the main elements of the coating layer vicinity of the positive electrode material of embodiment. It is a figure which shows the electron beam diffraction image of the coating compound containing Al of the positive electrode material of embodiment. It is a figure which shows the electron beam diffraction image of the coating compound containing P of the positive electrode material of embodiment. It is a figure which shows the outline of the secondary battery system carrying the lithium secondary battery produced in embodiment.

  Hereinafter, the characteristics of the positive electrode material for a lithium secondary battery, the lithium secondary battery, and the secondary battery module according to the present invention will be described.

  The positive electrode material for a lithium secondary battery according to the present invention is selected from the group consisting of a phosphoric acid compound and A (A is Mg, Al, Ti, Cu on the surface of the lithium manganese composite oxide of the positive electrode material having a layered structure. And an oxide or fluoride containing one or more elements), and P in the phosphoric acid compound is a surface layer side (electrolyte) of the coating layer in the coating layer. The atomic concentration on the side) is higher than the atomic concentration on the lithium manganese composite oxide side. Here, the oxide or fluoride containing A can be uniformly coated on the surface of the lithium manganese composite oxide. On the other hand, it is difficult for a phosphoric acid compound alone to coat the surface uniformly. Therefore, the phosphoric acid compound is uniformly distributed on the surface of the lithium manganese composite oxide by interposing an oxide or fluoride containing A. By forming the coating layer having such a configuration, the phosphoric acid compound having a large effect of suppressing the oxidative decomposition of the electrolytic solution can exert its role to the maximum and improve the thermal stability.

The lithium secondary battery according to the present invention, a lithium ion (Li ⁺⁾ capable of occluding and releasing cathode, a lithium secondary lithium ion (Li ⁺⁾ and capable of absorbing and releasing the negative electrode, but is formed through the electrolyte In the battery, the positive electrode is a lithium manganese composite oxide having a layered structure, and a phosphoric acid compound and A (A is selected from the group consisting of Mg, Al, Ti, Cu on the surface of the lithium manganese composite oxide) An oxide or fluoride containing one or more elements), and P in the phosphoric acid compound is a surface layer side (electrolyte side) of the coating layer in the coating layer The atomic concentration of is higher than the atomic concentration on the lithium manganese composite oxide side.

The lithium-manganese composite oxide, the group consisting of composition formula _{LiMn x M 1-x O 2} ( where, 0.1 ≦ x ≦ 0.6.M is Li, Mg, Al, Ti, Co, Ni, Mo) And one or more selected elements).

Furthermore, it is preferable that the phosphoric acid compound forming the coating layer is one or more selected from the group consisting of Li ₃ PO ₄ , Li ₄ P ₂ O ₇ and LiPO ₃ . The content of the phosphoric acid compound is preferably 0.1% by weight or more and 5.0% by weight or less with respect to the lithium manganese composite oxide (when the lithium manganese composite oxide is 100% by weight).

  The content of the oxide or fluoride containing A forming the coating layer is 0.2% by weight or more with respect to the lithium manganese composite oxide (when the lithium manganese composite oxide is 100% by weight). It is preferable that it is 1.5 weight% or less.

  And it is preferable that the thickness of the coating layer formed in the surface of the lithium manganese complex oxide of positive electrode material is 2 nm or more and 80 nm or less.

  Furthermore, the lithium secondary battery according to the present invention is characterized in that a main peak of heat generation is 230 ° C. or higher when a positive electrode charged to 4.8 V is heated with a Li counter electrode.

  The secondary battery module according to the present invention is a secondary battery module having a plurality of electrically connected batteries, and a control device that manages and controls the state of the plurality of batteries. The apparatus detects a voltage between terminals of each of the plurality of batteries, and each of the plurality of batteries constitutes a laminate having a positive electrode, a negative electrode, and an electrolyte in a battery can, and the positive electrode is a lithium manganese composite An oxide containing a phosphoric acid compound and A (A is one or more elements selected from the group consisting of Mg, Al, Ti, Cu) on the surface of the lithium manganese composite oxide Or P in the phosphoric acid compound has an atomic concentration on the surface layer side (electrolyte side) of the coating layer in the lithium manganese composite oxide side. Than the atomic concentration of And said that no.

  Next, one of the forms for implementing this invention is demonstrated in detail.

<Configuration of lithium secondary battery 10>
FIG. 1 is a schematic longitudinal sectional view showing a lithium secondary battery (18650 type lithium ion secondary battery) 10.

  In the lithium secondary battery 10, a separator 3 such as a microporous thin film that prevents contact between the positive electrode 1 and the negative electrode 2 and has ion conductivity is interposed between the positive electrode 1 and the negative electrode 2. The positive electrode 1, the negative electrode 2 and the separator 3 are overlapped and wound spirally, and are enclosed in a battery can 4 made of stainless steel or aluminum together with a non-aqueous electrolyte using an organic solvent.

  The positive electrode 1 is formed with a positive electrode lead 7 for extracting current, while the negative electrode 2 is formed with a negative electrode lead 5 for extracting current. As a result, currents generated in the positive electrode 1 and the negative electrode 2 are respectively extracted from the positive electrode 1 by the positive electrode lead 7 and are extracted from the negative electrode 2 by the negative electrode lead 5.

  In order to prevent short circuit between the positive electrode 1 and the negative electrode lead 5 and between the negative electrode 2 and the positive electrode lead 7, respectively, an insulating plate 9 having an insulating property such as an epoxy resin is formed. Further, between the battery can 4 in contact with the negative electrode lead 5 and the lid portion 6 in contact with the positive electrode lead 7, leakage of the electrolyte is prevented, and the positive electrode 1 of the positive electrode and the negative electrode 2 of the negative electrode. A packing (seal material) 8 such as rubber having electrical insulating properties is formed.

<Positive electrode 1>
The positive electrode 1 is formed by applying a positive electrode mixture to a current collector such as aluminum or copper (for example, an aluminum foil having a thickness of 5 μm or more and 25 μm or less, a copper foil having a thickness of about 10 μm, etc.) on one side, for example, about 100 μm thick. It is formed. The positive electrode mixture includes an active material described later that contributes to the intercalation / de-intercalation of lithium, a conductive material for increasing the conductivity of the positive electrode 1, and PVDF ( A binder such as polyvinylidene fluoride).

<Negative electrode 2>
The negative electrode 2 is formed by applying a negative electrode mixture on a current collector made of copper or the like (for example, a copper foil having a thickness of 7 μm or more and 20 μm or less) to a thickness of, for example, about 100 μm. The negative electrode mixture includes an active material, a conductive material, a binder, and the like. As the active material of the negative electrode 2, metallic lithium, a carbon material, and a material capable of inserting lithium or forming a compound can be used, and a carbon material is particularly preferable. Examples of the carbon material include graphites such as natural graphite and artificial graphite, and amorphous carbon such as coal-based coke, coal-based pitch carbide, petroleum-based coke, petroleum-based pitch carbide, and pitch-coke carbide.

  Preferably, these carbon materials are subjected to various surface treatments. These carbon materials can be used not only in one kind but also in combination of two or more kinds.

In addition, as materials capable of inserting lithium ions (Li ⁺ ) or forming compounds, metals such as aluminum, tin, silicon, indium, gallium, and magnesium and alloys containing these elements, metals including tin, silicon, and the like An oxide is mentioned. Furthermore, composite materials of these metals, alloys, metal oxides, and graphite-based or amorphous carbon materials can be mentioned.

<Coating layer covering lithium manganese composite oxide of positive electrode 1>
The active material of the positive electrode 1 is selected from the group consisting of a phosphoric acid compound and A (A is Mg, Al, Ti, Cu) on the surface of a lithium manganese composite oxide (hereinafter referred to as “composite oxide”). An oxide or fluoride containing one or more elements), and P in the phosphoric acid compound is a surface layer side (electrolyte side) of the coating layer in the coating layer It is preferable to use one having a higher atomic concentration than the atomic concentration on the lithium manganese composite oxide side.

  The phosphate compound has a role of suppressing the oxidative decomposition of the electrolytic solution in the vicinity of the positive electrode at a high voltage, and the effect is exhibited even when the phosphate compound is coated alone. However, by using together with an oxide or fluoride containing A (A is one or more elements selected from the group consisting of Mg, Al, Ti, Cu) and optimizing the arrangement of both, The effect is dramatically increased. P in the phosphoric acid compound preferably has an atomic concentration on the surface layer side (electrolyte side) higher than that on the complex oxide side of the coating layer in the coating layer.

  The element A contained in the coating layer is Mg, Al, Ti, Cu, but these oxides or fluorides can uniformly coat the complex oxide surface with a thin film, and selectively in the coating layer. A can be arranged in the vicinity of the complex oxide. Then, by coating the phosphoric acid compound from above, it is possible to uniformly dispose the phosphoric acid compound that is difficult to coat on the surface of the composite oxide alone.

  An oxide or fluoride containing A (A is one or more elements selected from the group consisting of Mg, Al, Ti, and Cu) also suppresses the oxidative decomposition of the electrolyte near the positive electrode at high voltage. Although it has a role, its effect is small compared to a phosphate compound. Therefore, the arrangement is different from that of the phosphoric acid compound, and in the coating layer, the atomic concentration on the composite oxide side is preferably higher than the atomic concentration on the surface layer side (electrolyte side).

  The distribution in the coating layer is divided into two from the central portion in the thickness direction, that is, from the interface on one side of the coating layer to the composite oxide side to the interface on the other side of the coating layer electrolyte (electrolyte). The interface side with the composite oxide as the positive electrode material is regarded as the composite oxide side, while the interface side with the electrolytic solution (electrolyte) is regarded as the surface layer side (electrolyte side), and the atomic concentration Is an average value of each divided range. The high atomic concentration was defined as the case where the average atomic concentration on the surface layer side (electrolyte side) was higher than the average atomic concentration on the composite oxide side by 4 atom% or more in consideration of measurement errors and the like.

The phosphoric acid compound forming the coating layer may be at least one selected from the group consisting of Li ₃ PO ₄ , Li ₄ P ₂ O ₇ , and LiPO ₃ from the viewpoint of suppressing the oxidative decomposition of the electrolyte solution described above. preferable.

One or more selected from the group consisting of LiMg _x M _1-x O ₂ (where 0.1 ≦ x ≦ 0.6, where M is Li, Mg, Al, Ti, Co, Ni, Mo) It is preferable to use those represented by (element). LiMn _x M _1-x O ₂ has a hexagonal layered structure, and the lithium diffusion path is two-dimensional with a gap between crystal lattices. On the other hand, in the orthorhombic olivine structure represented by LiFePO ₄ , the lithium diffusion path is a one-dimensional gap in the crystal lattice. Therefore, LiMn _x M _1-x O ₂ has an advantage that Li conductivity is high because the diffusion path of lithium is two-dimensional.

  It is preferable that Mn be included as the transition metal because the transition metal is responsible for charge compensation accompanying Li insertion / extraction. The transition metal becomes tetravalent when Li is completely removed during charging, but Mn is stable in tetravalent state, so that a stable crystal structure can be maintained even in a charged state. However, if the amount of Mn is less than 0.1, it cannot contribute to the structural stabilization. On the other hand, if it exceeds 0.6, it becomes difficult to maintain the layered structure itself. x ≦ 0.6 is preferred. More preferably, 0.2 ≦ x ≦ 0.4.

  In addition to Mn, transition metals include Ti, V, Cr, Fe, Co, Ni, Cu, Nb, Mo, and the like. Elements that form a layered structure by forming a composite oxide with lithium include Ti, Ni. , Co, and Mo are preferable.

In addition, it is known that a positive electrode material having a layered structure has a lithium diffusion path inhibited by site (position) exchange between lithium and a transition metal, and the conductivity of lithium ions (Li ⁺ ) is lowered. Here, site exchange between lithium and the transition metal can be suppressed by substituting a part of the transition metal with a typical element whose valence does not change. In the present invention, the ratio of site (position) exchange between lithium and the transition metal can be reduced by using monovalent lithium, divalent magnesium, and trivalent aluminum as substitution elements.

  Although the amount of oxygen (O) is defined as 2, it is known that the amount of oxygen (O) deviates somewhat from the stoichiometric composition depending on the firing conditions. Therefore, it is not deviated from the gist of the present invention that the oxygen amount is about 5%.

  In order to obtain a composite oxide having excellent thermal stability in a charged state, in addition to the arrangement of the coating compound (coating layer) covering the composite oxide and the composition of the composite oxide, the content of the coating compound forming the coating layer Is also an important point.

  The content of the phosphoric acid compound forming the coating compound (coating layer) is 0.1 wt% or more and 5.0 wt% or less with respect to the composite oxide of the positive electrode material (when the composite oxide is 100 wt%). It is preferable that

  The phosphoric acid compound in the coating layer has a role of suppressing the oxidative decomposition of the electrolytic solution, and if the content of the phosphoric acid compound is less than 0.1% by weight, the complex oxide surface cannot be entirely covered, so that the role is sufficient Can not fulfill. On the other hand, when the amount exceeds 5.0% by weight, the phosphorus compound itself does not contribute to the charge / discharge reaction, which results in a decrease in battery capacity. Therefore, it is more preferably 0.5% by weight or more and 2.0% by weight or less of the central region of these numerical values.

  The content of oxide or fluoride containing M (M is one or more elements selected from the group consisting of Mg, Al and Cu) forming the coating compound (coating layer) is (When the composite oxide is 100% by weight) is preferably 0.2% by weight or more and 1.5% by weight or less.

  Here, the oxide or fluoride containing M has a role of an intervening layer for covering the surface of the composite oxide with the phosphate compound, and therefore covers the composite oxide over the entire surface. It is preferable. Therefore, if it is less than 0.2% by weight, the amount is so small that it cannot be said to be sufficient for coating the surface of the composite oxide. On the other hand, when it exceeds 1.5% by weight, the oxide or fluoride itself containing M is an insulator, so that the resistance of the positive electrode increases and the loss increases, resulting in a significant decrease in battery capacity. Therefore, more preferably, it is 0.4 wt% or more and 1.0 wt% or less of the central region of these numerical values.

  Moreover, it is preferable that the thickness of the coating layer which coat | covers complex oxide is 2 nm or more and 80 nm or less. When the thickness of the coating layer is less than 2 nm, it is necessary to make the particle size of the coating compound itself smaller, and the coating compound particles forming the coating layer are aggregated by van der Waals force to make the composite oxide surface uniform. It becomes difficult to coat. On the other hand, if the thickness of the coating layer exceeds 80 nm, the resistance increase due to the coating layer becomes more significant than the effect of improving the thermal stability during charging, and the loss increases, resulting in deterioration of battery characteristics. More preferably, it is 10 nm or more and 60 nm or less in the central region of these numerical values.

<Surface coating treatment with composite oxide coating layer>
In order to form a coating compound (coating layer) on the surface of the composite oxide, a surface coating treatment is required. In the present invention, the coating compound includes a phosphate compound and an oxide or fluoride containing A (A is one or more elements selected from the group consisting of Mg, Al, Ti, and Cu). .

  And P in the phosphoric acid compound of the coating compound needs to have an atomic concentration on the surface layer side (electrolyte side) higher than that on the complex oxide side in the coating layer. Therefore, the procedure of coating treatment for the composite oxide is important.

  The method for surface treatment of the composite oxide is roughly classified into a solid phase method and a liquid phase method, but a liquid phase method is preferable. In the solid phase method, it is difficult to uniformly disperse the coating compound (coating layer) on the surface of the composite oxide, and there is a concern about physical damage on the surface of the composite oxide accompanying the coating treatment. On the other hand, the advantages of the liquid phase method are that the surface of the composite oxide can be uniformly covered, the particle size of the coating layer can be controlled, and the surface of the composite oxide can be physically damaged. There is small nature.

  In order to increase the atomic concentration of P in the phosphoric acid compound in the vicinity of the surface layer side (electrolyte side) in the coating layer, the composite oxide was coated by the following procedure.

  First, a hydroxide containing A was produced in a solvent and mixed with the composite oxide. Then, the phosphoric acid compound was thrown into the solvent and mixed at room temperature. By mixing in such a procedure, the hydroxide containing water molecules first adheres to the surface of the composite oxide. At this time, since the hydroxide contains OH groups and has high wettability, it adheres well to the surface of the composite oxide. Thereafter, the phosphoric acid compound adheres to the hydroxide. When the solvent is evaporated by vacuum drying or spray drying in this state, and the obtained powder is heat-treated in the atmosphere, the hydroxide containing A becomes the oxide containing A.

  Alternatively, when the heat treatment is performed in a fluorine gas atmosphere, the hydroxide containing A becomes a fluoride containing A. By processing in this way, the atomic concentration of P in the phosphoric acid compound can be increased in the vicinity of the surface layer side (electrolyte side) in the coating layer. On the other hand, A tends to have an atomic concentration in the vicinity of the composite oxide higher than the atomic concentration on the surface layer side (electrolyte side).

  A coating layer containing a phosphoric acid compound and an oxide or fluoride containing A (A is one or more elements selected from the group consisting of Mg, Al, Ti, and Cu) on the surface of the composite oxide In the coating layer, P in the phosphoric acid compound indicates that the atomic concentration on the surface layer side (electrolyte side) of the coating layer is higher than the atomic concentration on the composite oxide (lithium manganese composite oxide) side of the coating layer. The featured positive electrode material for a lithium secondary battery may be used alone. Alternatively, this positive electrode material for a lithium secondary battery may be used by mixing with an uncoated composite oxide, or a positive electrode material having a spinel structure or an olivine structure.

  The lithium secondary battery of the present invention has a main peak of heat generation of 230 ° C. or higher, preferably 250 ° C. or higher, when a positive electrode charged to 4.8 V with a Li counter electrode is heated.

<Method for producing composite oxide>
Next, a method for producing a composite oxide (lithium manganese composite oxide) will be described.

  The following can be used as raw materials for the composite oxide.

Examples of the lithium compound include lithium carbonate (Li ₂ CO ₃ ), lithium hydroxide (LiOH), lithium nitrate (LiNO ₃ ), lithium acetate (CH ₃ CO ₂ Li), lithium chloride (LiCl), and lithium sulfate (Li ₂ SO ₄ ) and the like can be used, and lithium carbonate (Li ₂ CO ₃ ) and lithium hydroxide (LiOH) are preferred.

Manganese compounds include manganese hydroxide (Mn (OH) ₃ ), manganese carbonate (Mn ₂ (CO ₃ ) ₃ ), manganese nitrate (Mn (NO ₃ ) ₃ ), manganese acetate (Mn (CH ₃ CO ₂ ) ₃ ), Manganese sulfate (Mn ₂ (SO ₄ ) ₃ ), manganese oxide (MnO), and the like can be used, and manganese carbonate (Mn ₂ (CO ₃ ) ₃ ) and manganese oxide (MnO) are preferable.

  Examples of the compound of the substitution element M include hydroxides, carbonates, nitrates, acetates, sulfates, oxides and the like.

The raw material is supplied as a powder having a predetermined composition ratio, which is pulverized and mixed by a mechanical method such as a ball mill. For pulverization and mixing, either a dry method or a wet method may be used. The obtained powder is fired at 700 ° C. or higher and 1000 ° C. or lower, preferably 800 ° C. or higher and 900 ° C. or lower. The firing time is preferably 4 to 48 hours, more preferably 10 to 24 hours. The atmosphere for firing is preferably an oxidizing gas (O ₂ ) atmosphere such as oxygen or air. After calcination, it may be air-cooled, gradually cooled in an inert gas (nitrogen, argon gas, etc.) atmosphere, or rapidly cooled using liquid nitrogen or the like. Further, the firing may be repeated twice or more.

  By doing in this way, oxygen deficiency from the complex oxide surface can be suppressed. The average secondary particle size of the powder obtained after firing is preferably 1 μm or more and 20 μm or less. If the thickness is less than 1 μm, the specific surface area is too large, and a sufficient electron conductive path cannot be ensured during electrode production. On the other hand, if the thickness exceeds 20 μm, the Li diffusion path in the composite oxide becomes long, which is disadvantageous for lithium occlusion and release. More preferably, it is 4 μm or more and 15 μm or less in the central region of these numerical values.

  Using the composite oxide thus obtained, a surface treatment is then performed.

<Method for surface treatment of composite oxide>
Hereinafter, a surface treatment method of a composite oxide (lithium manganese composite oxide) by a liquid phase method will be described.

A predetermined amount of nitrate, acetate, or sulfate containing a metal element selected from the group of Mg, Al, Ti, and Cu is dissolved in water or an organic solvent. And it adjusts with a pH adjuster so that pH of a solvent may become equivalent to complex oxide (lithium manganese complex oxide). Here, the pH of the composite oxide is the pH of the supernatant when 10 g of the composite oxide is added to 100 ml of pure water, stirred for 10 minutes at room temperature, and then allowed to stand for 20 minutes. The pH of the composite oxide varies depending on the composition, but is approximately between pH 8 and pH 11. As the pH adjuster, alkaline lithium hydroxide (LiOH) or ammonia (NH ₃ ) water can be used, but lithium hydroxide (LiOH) is preferably used. By using lithium hydroxide to make the pH of the composite oxide within a range of about ± 0.5 to make an alkaline solution, a metal element raw material (a metal element selected from the group of Mg, Al, Ti, Cu) The nitrates, acetates, and sulfates that it contains) precipitate as hydroxide metals.

For example,
Al (NO ₃ ) ₃ + 3H ₂ O → Al (OH) ₃ + 3HNO ₃
The positive electrode material described above was mixed in the solvent adjusted in this way, and the coating compound was adhered to the surface. Next, diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) or ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ) is used as a raw material for the phosphoric acid compound in the same type of solvent as used above. Dissolve a predetermined amount. Further, when a predetermined amount of LiOH is added, the phosphate compound raw material (diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ), ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ), etc.) It becomes and precipitates.

For example,
(NH ₄ ) ₂ HPO ₄ + 3LiOH → Li ₃ PO ₄ + NO ₃ ⁻ + 5H ₂
The solvent thus obtained was added to a mixed solution of hydroxide metal and composite oxide, and then the solvent was evaporated. The solvent is preferably evaporated by heating and stirring or spray drying. Finally, the obtained powder is heat-treated at 300 ° C. to 800 ° C., more preferably 500 ° C. to 700 ° C. By heating, the hydroxide (for example, Al (OH) ₃ ) adhering to the surface of the complex oxide becomes an oxide (for example, Al ₂ O ₃ ), and further, the complex compound and the coating compound (coating layer) are oxidized. Strong adhesion can be imparted between objects. The heating time is 1 hour or more and 20 hours or less, preferably 3 hours or more and 8 hours or less.

Alternatively, the hydroxide (eg, Al (OH) ₃ ) can be changed to fluoride (eg, AlF ₃ ) by performing the heat treatment in a fluorine (F ₂ ) gas atmosphere. As the fluorine gas, nitrogen trifluoride (NF ₃ ) gas is preferable.

(Confirmation of crystal structure)
The crystal structure of the produced composite oxide (lithium manganese composite oxide) was measured for a diffraction profile with a radiation source CuKα using an automatic X-ray diffractometer (RINT-Ultima III, hereinafter referred to as XRD) manufactured by Rigaku Corporation.

  The crystal structure of the composite oxide was confirmed from the peak angle of the obtained diffraction profile.

(Measurement method of average particle size of positive electrode material)
The average particle size of the positive electrode material was measured by a laser diffraction / scattering method as follows using a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.).

  First, as a dispersant, a mixture of pure water and 0.2 wt% sodium hexametaphosphate was used, and a positive electrode material was charged. In order to suppress aggregation of the material, after applying ultrasonic waves for 5 minutes and separating by vibration, the median diameter (particle diameter of particles having a relative particle amount of 50%) was measured to obtain an average particle diameter.

(Confirmation of element distribution in coating layer)
The thickness of the coating layer and the concentration distribution of atoms in the coating layer were measured by a field emission transmission electron microscope (hereinafter abbreviated as TEM) equipped with an X-ray analyzer (hereinafter abbreviated as EDS) (NORAN System 300 manufactured by Thermo Fisher). ) (Manufactured by Hitachi, Ltd., HF-2000) at an acceleration voltage of 200 kV. The sample was sliced in advance by an Ar ion etching method using a polishing machine (600 type manufactured by GATAN).

  In addition to this, the element distribution of the coating layer includes TEM-EELS combining TEM and electron energy loss spectroscopy (EELS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), Auger electron spectroscopy (AES) Etc. can be confirmed.

(Confirmation of coating compound (coating layer))
The bonding state of the surface coating compound (coating layer) is TEM (manufactured by Hitachi, Ltd. HF-2000), an electron beam diffraction image is acquired at an accelerating voltage of 200 kV, and the diffraction point is the diffraction point of a known compound in the attached database. The compound type was determined by comparison with the above information.

(Measurement method of weight ratio of elements)
The weight ratio of the elements used for the surface treatment for forming the coating layer was measured using a high frequency inductively coupled plasma emission spectroscopy (hereinafter abbreviated as ICP) analyzer (P-4000 manufactured by Hitachi, Ltd.). First, 5 g of positive electrode material and 2 ml of nitric acid were added to 45 ml of ion exchange water in a beaker, and the mixture was stirred for 30 minutes with a stirrer (stirrer). After standing for 5 minutes, the furnace liquid filtered with filter paper was sprayed into a high-frequency atmosphere together with argon gas, and the light intensity specific to each excited element was measured to calculate the weight ratio of the elements.

(Measurement method of exothermic peak)
The calorific value at the time of temperature increase was evaluated with a differential scanning calorimeter (manufactured by Seiko Instruments Inc .: DSC6100, hereinafter abbreviated as DSC). First, a positive electrode charged to a predetermined voltage was prepared after initialization in a model cell for electrochemical property evaluation, and punched out to a diameter of 4 mm in a glove box in an argon atmosphere. Two pieces of this were put into a sample pan made of SUS, about 2 μl of the electrolyte was added, and sealed with a caulking machine. Thereafter, the sample chamber was heated from 30 to 400 ° C. at a rate of temperature increase of 5 ° C./min in an argon atmosphere using a DSC apparatus, and the heat generation behavior was measured.
<Method for producing lithium secondary battery>
An example of a method for producing a lithium secondary battery is as follows.

  A positive electrode material (composite oxide) of the active material is mixed with a conductive material of carbon material powder and a binder such as polyvinylidene fluoride to produce a slurry. The mixing ratio of the conductive material to the positive electrode material (when the positive electrode material is 100% by weight) is preferably 3% by weight or more and 10% by weight or less.

  The mixing ratio of the binder to the positive electrode material (when the positive electrode material is 100% by weight) is preferably 2% by weight or more and 10% by weight or less.

  In mixing, in order to uniformly disperse the positive electrode material in the slurry, it is preferable to perform sufficient kneading using a kneader.

  The obtained slurry is coated on both sides of a current collector aluminum foil having a thickness of 15 μm or more and 25 μm or less by, for example, a roll transfer machine. After coating on both sides, the electrode plate of the positive electrode 1 (see FIG. 1) is formed by press drying. The thickness of the mixture portion in which the positive electrode material, the conductive material, and the binder are mixed is desirably 200 μm or more and 250 μm or less.

  As with the positive electrode, the negative electrode is mixed with a binder and applied to a current collector and then pressed to form an electrode. Here, the thickness of the electrode mixture is preferably 20 μm or more and 70 μm or less. In the case of the negative electrode, a copper foil having a thickness of 7 μm to 20 μm is used as the current collector. The mixing ratio of application is preferably 90:10 in terms of the weight ratio of the negative electrode material and the binder, for example.

The positive electrode and the negative electrode pressed after application of the mixture are cut to a predetermined length to form the positive electrode 1 and the negative electrode 2 shown in FIG. 1, and the positive electrode lead 7 and the negative electrode lead 5 of the current drawing tab portion are spot welded respectively. Or it forms by ultrasonic welding. The positive electrode lead 7 and the negative electrode lead 5 in the tab portion are each made of a metal foil made of the same material as the rectangular current collector, and are members installed to take out current from the electrodes. Between the tabbed positive electrode 1 and negative electrode 2, an ion-conductive microporous membrane that allows L ⁺ ions to pass therethrough, for example, a separator 3 made of polyethylene (PE), polypropylene (PP) or the like is sandwiched and stacked. As shown in FIG. 1, the electrode group is formed in a cylindrical shape (spiral shape) and stored in a battery can 4 in a cylindrical container.

  Alternatively, although not shown, a separator having a bag shape may be used to store the electrodes therein, and these may be sequentially stacked and stored in a rectangular container as a multilayer structure. The material of the container is preferably stainless steel or aluminum. Since a passive film is formed on the surface of stainless steel, it is difficult to corrode, and since it is steel, it has high strength and can withstand the increase in the internal pressure of the gas evaporated from the electrolyte in the battery can 4. Aluminum is characterized by its high energy density per weight due to its light weight.

  After the electrode group (positive electrode 1, negative electrode 2, separator 3) is stored in the battery can 4 of the battery container, an electrolyte is injected into the battery can 4 of the battery container and sealed with the packing 8 to complete the battery.

The electrolytes include diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), methyl acetate (MA), ethyl methyl carbonate (EMC), methyl propyl A solution in which lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium perchlorate (LiClO ₄ ) or the like is dissolved as an electrolyte in a solvent such as carbonate (MPC) is used. desirable. The electrolyte concentration is preferably 0.7 M (mol) or more and 1.5 M (mol) or less.

  In addition, a compound having a carboxylic anhydride group, a compound having a sulfur element (S) such as propane sultone, or a compound having boron (B) may be mixed in these electrolytic solutions. The purpose of adding these compounds is to suppress the reductive decomposition of the electrolytic solution on the surface of the negative electrode 2, to prevent reduction precipitation of metal elements such as manganese eluted from the positive electrode 1 on the negative electrode 2, to improve the ionic conductivity of the electrolytic solution, What is necessary is just to select according to the objectives, such as a flame retardant of a liquid.

  Hereinafter, examples will be described in more detail, but the present invention is not limited to these examples.

  Table 1 shows the characteristics of the composite oxide of the positive electrode manufactured in Example 1.

(Production of positive electrode material)
In Example 1, lithium carbonate (LiCO ₃ ), manganese oxide (MnO ₂ ), nickel oxide (NiO), and cobalt oxide (CoO) are used as raw materials for the composite oxide, and Li: Mn: Ni: Co in the raw material ratio. However, 1.04: 0.20: 0.38: 0.38 was weighed and wet pulverized and mixed with a pulverizer. After the powder was dried, it was put into a high-purity alumina container, pre-fired at 600 ° C. for 10 hours in the atmosphere to improve the sinterability, and air-cooled. Next, the calcined powder was pulverized, put again into a high-purity alumina container, subjected to main calcination in the atmosphere at 900 ° C. for 16 hours, air-cooled, and crushed and classified.

The X-ray diffraction profile of the obtained composite oxide is shown in FIG. The obtained peak was collated with an International Center for Diffraction Data card (hereinafter referred to as an ICDD card) (PDF-2), and confirmed to have a hexagonal layered structure. Therefore, the composition of the composite oxide is LiMn _0.20 (Li _0.04 Ni _0.38 Co _0.38 ) O ₂ . Further, when the particle size distribution of the composite oxide was measured, the average secondary particle size was 5 μm.

  Next, the surface treatment process will be described.

Aluminum nitrate _{(Al (NO 3) 3 ·} 9H 2 O) composite oxide produced in 3.0g and lithium hydroxide (LiOH · H ₂ O) Ion-exchanged water 100ml was dissolved 1.0g were charged at normal temperature The aluminum compound was adhered to the surface of the composite oxide by stirring for 1 hour. Next, 1.0 g of diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) and 100 ml of ion-exchanged water in which 1.0 g of lithium hydroxide is dissolved are added, and the mixture is stirred for 1 hour at room temperature. An acid compound was deposited. And this solution was dried with the spray dryer, the obtained powder was put into the high purity alumina container, and it heated at 650 degreeC in air | atmosphere for 5 hours.

  The obtained surface-modified composite oxide was pretreated by ion milling and observed by TEM. As a result, the thickness of the coating layer was about 30 nm (see Table 1 and FIG. 3). Further, FIG. 3 shows the result of line analysis of the distribution of main elements in the vicinity of the coating layer.

  FIG. 3 shows that the interface between the composite oxide and the coating layer in the positive electrode has a distance of 0 nm, and the distance of −40 nm to 0 nm is equivalent to the composite oxide because the atomic concentrations of O (oxygen) and (Mn + Ni + Co) are almost constant It turns out that it is a part to do.

  From a distance of 0 nm to a distance of 30 nm, the atomic concentration of Mn became 0 and O (oxygen) also decreased, and the atomic concentrations of P and Al appeared instead. This portion corresponds to the coating layer, and the atomic concentration of P gradually increases from a distance of 0 nm to a distance of 30 nm. That is, in the coating layer, it was found that P has an atomic concentration on the surface layer side (electrolyte side) of the coating layer higher than that on the complex oxide side in the coating layer. Dividing the coating layer into two parts from the central portion (near 15 nm) in the thickness direction from the surface layer side (electrolyte side) to the composite oxide side, and averaging the atomic concentration of P on the composite oxide side and the surface layer side (electrolyte side) The surface layer side (electrolyte side) side was 9 atom% (see Table 1), and the composite oxide side was 3 atom% (see Table 1).

4 and 5 show electron diffraction line images of the P compound and the Al compound in the coating layer. When these figures are compared with the information of electron diffraction line images of known P compounds and Al compounds in the database based on the detected elements, Li ₃ of No. 15-760 of ICDD (International Center for Diffraction Data), respectively. It was found to be consistent with γ-Al ₂ O _{3 of} PO ₄ and No. 10-425.

Further, as a result of ICP analysis of the composite oxide after surface modification, the weight ratio of P and Al to the composite oxide is about 1.0% by weight when calculated by Li ₃ PO ₄ and γ-Al ₂ O ₃ , respectively. (See Table 1), about 0.4 wt% (see Table 1) was found to be coated.

  Next, production of a test battery will be described.

(Preparation of positive electrode for test battery)
Using the obtained surface-modified composite oxide, a positive electrode of a test battery was produced. A composite oxide, a carbon-based conductive material, and a binder previously dissolved in N-methyl-2-pyrosinone (NMP) as a solvent are mixed in a ratio of 85: 10: 5 in mass percent, and uniformly mixed. The mixed slurry was applied onto an aluminum foil current collector having a thickness of 20 μm. Then, it dried at 120 degreeC and compression-molded so that the electrode density might be set to 2.7 g / cm < ³ > with a press. After compression molding, a positive electrode for a test battery was manufactured by punching into a disk shape having a diameter of 15 mm using a punched metal fitting.

(Production of test battery)
Using the produced positive electrode, a mixed solvent of EC (ethylene carbonate), DMC (dimethyl carbonate), and VC (vinylene carbonate) with metallic lithium as a negative electrode and 1.0 mol of LiPF ₆ as an electrolyte, A test battery was prepared.

  Exothermic peak evaluation using this test battery will be described.

  The exothermic peak of the positive electrode of the test battery was evaluated by the following procedure. After charging at a constant current / constant voltage up to 4.2 V with a charge rate of 0.5 C (speed of completing 100% charge in 2 hours), a discharge rate of 0.5 C (100 in 2 hours) is reached. % Discharge at a constant rate).

  This was repeated three times as one cycle of charging and discharging, and then charged at a constant current / constant voltage up to 4.8 V with a charging rate of 0.5 C. Thereafter, the test battery was disassembled, the positive electrode was taken out, and the exothermic behavior was measured by DSC. As a result, an exothermic peak appeared at 265 ° C. (see Table 1).

<Production of 18650 type battery>
The production of an 18650 (diameter 18 mm × height 650 mm) type battery will be described.

  A 18650 type battery was fabricated using the obtained positive electrode material. First, a composite oxide, a conductive material of carbon material powder, and a binder of PVdF (polyvinylidene fluoride) are mixed at a weight ratio of 90: 5: 5, and an appropriate amount of NMP (N-methylpyrrolidone) is added. In addition, a slurry was prepared.

  The prepared slurry was stirred for 3 hours with a planetary mixer and kneaded.

Next, the kneaded slurry was applied to both surfaces of an aluminum foil having a thickness of 20 μm serving as a current collector of the positive electrode 1 using an applicator of a roll transfer machine. This was pressed with a roll press machine so that the mixture density was 2.70 g / cm ³ to obtain a positive electrode.

  Subsequently, when producing the negative electrode 2, using amorphous carbon as the negative electrode active material, carbon black as the conductive material, PVdF as the binder, and mixing at a weight ratio of 92: 2: 6, The mixture was stirred for 30 minutes with a slurry mixer.

  The kneaded slurry was applied to both sides of a 10 μm thick copper foil as a current collector of the negative electrode 2 using a coating machine, dried, and then pressed with a roll press to obtain a negative electrode.

  The positive electrode and the negative electrode were cut into predetermined sizes, and the positive electrode lead 7 and the negative electrode lead 5 of the current collecting tab were installed by ultrasonic welding on the uncoated portion of each electrode.

  The porous polyethylene film of the separator 3 was sandwiched between the positive electrode 1 and the negative electrode 2 and wound into a cylindrical shape (spiral shape), and then inserted into a 18650 type battery can 4.

  After connecting the positive electrode lead 7 of the current collecting tab and the lid 6 of the battery can 4, the lid 6 of the battery can 4 and the battery can 4 were welded by laser welding to seal the battery.

  Finally, a non-aqueous electrolyte was injected from the injection port provided in the battery can 4 to obtain an 18650 type battery (lithium secondary battery 10).

  Evaluation of energy density will be described.

  Evaluation of the energy density of the produced 18650 type battery was performed in the following procedures. A current of 0.5 C was passed to charge a constant current to a charge end voltage of 4.2 V, and after a pause of 1 hour, a constant current was discharged to 2.7 V at the same current value. The energy density was calculated by dividing the discharge capacity at this time by the battery weight. The test environment temperature was 25 ° C. The results are shown in Table 2.

In Example 2, a composite oxide is produced in the same manner as in Example 1, and the surface-modified composite oxidation is performed by performing the heat treatment after the surface treatment in a nitrogen trifluoride gas (NF ₃ ) atmosphere instead of in the air. A product was made.

The thickness of the coating layer of Example 2 is 30 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer is 9 atom%, while the average concentration on the complex oxide side is 3 atom%. Electron diffraction images of the coating compound containing P and Al in the coating layer were consistent with IC3 No. 15-760 Li ₃ PO ₄ and No. 10-425 γ-Al ₂ O ₃ , respectively. As a result of converting the composite oxide after surface modification from ICP analysis, the weight ratios of P and Al compounds in the coating layer to the composite oxide were 1.0% and 0.4%, respectively. The exothermic peak was 275 ° C.

  Table 3 shows the characteristics of the composite oxide produced in Example 2.

  In the same manner as in Example 1, a 18650 type battery was produced and the capacity retention rate was evaluated. The results are shown in Table 4.

  It can be seen that the battery using the positive electrode manufactured in Example 2 also has an energy density of 129 Ah / kg and exhibits high performance.

In this Example 3, a composite oxide was prepared in the same manner as in Example 1, and magnesium nitrate (Mg (NO ₃ ) ₂ ) was used instead of 3.0 g of aluminum nitrate and 1.0 g of lithium hydroxide as a raw material for surface treatment. A surface-modified composite oxide was produced using 7.5 g and 2.5 g of lithium hydroxide.

The thickness of the coating layer of Example 3 was 60 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer was 12 atom%, while the average concentration on the composite oxide side was 4 atom%. Electron diffraction images of the coating compound containing P and Al forming the coating layer were consistent with Li ₃ PO ₄ of ICDD No. 15-760 and γ-Al ₂ O ₃ of No. 10-425, respectively. As a result of converting the composite oxide after surface modification from ICP analysis, the weight ratios of P and Al compounds in the coating layer to the composite oxide were 2.0% and 1.0%, respectively.

  Table 3 shows the characteristics of the composite oxide prepared in Example 3.

  The exothermic peak was 290 ° C.

  In the same manner as in Example 1, a 18650 type battery was produced and the capacity retention rate was evaluated. The results are shown in Table 4.

  It can be seen that the battery using the positive electrode manufactured in Example 3 also has an energy density of 128 Ah / kg and exhibits high performance.

  In Example 4, a composite oxide (lithium manganese composite oxide) was prepared in the same manner as in Example 1, and aluminum nitrate 6 instead of 3.0 g of aluminum nitrate and 1.0 g of lithium hydroxide was used as a raw material for the surface treatment. Using 2.0 g of lithium hydroxide and 2.0 g of lithium hydroxide, instead of 1.0 g of diammonium hydrogen phosphate and 1.0 g of lithium hydroxide, using 1.2 g of diammonium hydrogen phosphate and 1.2 g of lithium hydroxide A surface modified composite oxide was prepared.

The thickness of the coating layer of Example 4 was 50 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer was 8 atom%, while the average concentration on the composite oxide side was 4 atom%. Electron diffraction images of the coating compound containing P and Al forming the coating layer were consistent with Li ₃ PO ₄ of ICDD No. 15-760 and γ-Al ₂ O ₃ of No. 10-425, respectively. As a result of converting the composite oxide after surface modification from ICP analysis, the weight ratios of P and Al compounds in the coating layer to the composite oxide were 1.2% and 0.8%, respectively.

  Table 3 shows the characteristics of the composite oxide produced in Example 4.

  The exothermic peak was 260 ° C.

  In the same manner as in Example 1, a 18650 type battery was produced and the capacity retention rate was evaluated. The results are shown in Table 4.

  It can be seen that the battery using the positive electrode produced in Example 4 also has an energy density of 130 Ah / kg and exhibits high performance.

In this Example 5, titanium oxide (TiO ₂ ) was used as a raw material for the composite oxide in addition to the raw material of Example 1, and Li: Mn: Ni: Co: Ti was 1.04: 0.40: A composite oxide was prepared in the same manner as in Example 1 by weighing so that 0.25: 0.25: 0.06. Thereafter, using 3.0 g of copper nitrate (Cu (NO ₃ ) ₂ ) and 2.0 g of lithium hydroxide instead of 3.0 g of aluminum nitrate and 1.0 g of lithium hydroxide as surface treatment materials, A surface-modified composite oxide was produced using 2.5 g of diammonium hydrogen phosphate and 2.5 g of lithium hydroxide instead of 1.0 g of ammonium and 1.0 g of lithium hydroxide.

The thickness of the coating layer of Example 5 was 60 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer was 12 atom%, while the average concentration on the composite oxide side was 4 atom%. Electron diffraction images of coating compounds containing P and Cu forming the coating layer were consistent with IC3 No. 15-760 Li ₃ PO ₄ and No. 5-661 CuO, respectively. As a result of converting the composite oxide after surface modification from ICP analysis, the weight ratios of P and Cu compounds in the coating layer to the composite oxide were 2.0% and 1.0%, respectively.

  Table 3 shows the characteristics of the composite oxide prepared in Example 5.

  The exothermic peak was 280 ° C.

  In the same manner as in Example 1, a 18650 type battery was produced and the capacity retention rate was evaluated. The results are shown in Table 4.

  It can be seen that the battery using the positive electrode manufactured in Example 5 also has an energy density of 136 Ah / kg and exhibits high performance.

In Example 6, molybdenum oxide (W ₂ O ₅ ) was used in addition to the raw material of Example 1 as a raw material for the composite oxide, and Li: Mn: Ni: Co: W was 1.04: 0. 33: 0.30: 0.30: 0.03 was weighed to produce a composite oxide in the same manner as in Example 1. Thereafter, 3.6 g of aluminum nitrate and 1.5 g of lithium hydroxide were used instead of 3.0 g of aluminum nitrate and 1.0 g of lithium hydroxide as surface treatment materials, and 1.0 g of diammonium hydrogen phosphate and lithium hydroxide were used. A surface-modified composite oxide was prepared using 1.5 g of diammonium hydrogen phosphate and 1.5 g of lithium hydroxide instead of 1.0 g.

The thickness of the coating layer of Example 6 was 30 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer was 10 atom%, while the average concentration on the composite oxide side was 5 atom%. Electron diffraction images of the coating compound containing P and Al forming the coating layer were consistent with Li ₃ PO ₄ of ICDD No. 15-760 and γ-Al ₂ O ₃ of No. 10-425, respectively. As a result of converting the composite oxide after surface modification from ICP analysis, the weight ratios of P and Al compounds in the coating layer to the composite oxide were 1.2% and 0.6%, respectively.

  Table 3 shows the characteristics of the composite oxide prepared in Example 6.

  The exothermic peak was 275 ° C.

  In the same manner as in Example 1, a 18650 type battery was produced and the capacity retention rate was evaluated. The results are shown in Table 4.

  It can be seen that the battery using the positive electrode produced in Example 6 also has an energy density of 128 Ah / kg and exhibits high performance.

In Example 7, magnesium oxide (MgO) was used as a raw material for the composite oxide in addition to the raw material of Example 1, and Li: Mn: Ni: Co: Mg was 1.04: 0.20: 0 in the raw material ratio. .32: 0.32: 0.02 was weighed to produce a composite oxide in the same manner as in Example 1. Then, instead of using 3.0 g of aluminum nitrate and 1.0 g of lithium hydroxide as the raw material for the surface treatment, 2.2 g of titanyl sulfate (TiOSO ₄ ) and 0.8 g of lithium hydroxide were used, and 1.0 g of diammonium hydrogen phosphate. A surface-modified composite oxide was prepared using 0.5 g of diammonium hydrogen phosphate and 0.5 g of lithium hydroxide instead of 1.0 g of lithium hydroxide.

The thickness of the coating layer of Example 7 was 20 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer was 7 atom%, while the average concentration on the composite oxide side was 3 atom%. Electron diffraction images of coating compounds containing P and Ti forming the coating layer were consistent with Li ₃ PO ₄ of ICDD No. 15-760 and TiO ₂ of No. 21-1272, respectively. As a result of converting the composite oxide after the surface modification from ICP analysis, the weight ratios of the P and ti compounds in the coating layer to the composite oxide were 0.5% and 0.4%, respectively.

  Table 3 shows the characteristics of the composite oxide prepared in Example 7.

  The exothermic peak was 250 ° C.

  In the same manner as in Example 1, a 18650 type battery was produced and the capacity retention rate was evaluated. The results are shown in Table 4.

  It can be seen that the battery using the positive electrode manufactured in Example 7 also has an energy density of 132 Ah / kg and exhibits high performance.

In Example 8, aluminum oxide (Al ₂ O ₃ ) was used as a raw material for the composite oxide in addition to the raw material of Example 1, and Li: Mn: Ni: Co: Al was 1.04: 0. A composite oxide was prepared in the same manner as in Example 1 by weighing so as to be 40: 0.25: 0.25: 0.06. Thereafter, a surface-modified composite oxide was produced using 3.0 g of magnesium nitrate (Mg (NO ₃ ) ₂ ) instead of 3.0 g of aluminum nitrate as a raw material for the surface treatment.

The thickness of the coating layer of Example 8 was 20 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer was 10 atom%, while the average concentration on the composite oxide side was 2 atom%. Electron diffraction images of the coating compounds containing P and Cu to form the coating layer respectively match the No.15-760 Li ₃ PO ₄ and Nanba45-946 MgO of the ICDD. As a result of converting the composite oxide after surface modification from ICP analysis, the weight ratios of P and Mg compounds in the coating layer to the composite oxide were 1.0% and 0.4%, respectively.

  Table 3 shows the characteristics of the composite oxide prepared in Example 8.

  The exothermic peak was 260 ° C.

  In the same manner as in Example 1, a 18650 type battery was produced and the capacity retention rate was evaluated. The results are shown in Table 4.

  It can be seen that the battery using the positive electrode manufactured in Example 8 also has an energy density of 127 Ah / kg and exhibits high performance.

  In this Example 9, a composite oxide was prepared in the same manner as in Example 1, and instead of using 3.0 g of aluminum nitrate and 1.0 g of lithium hydroxide as a raw material for surface treatment, 11.2 g of aluminum nitrate and 3 of lithium hydroxide were used. Using 0.8 g, instead of 1.0 g of diammonium hydrogen phosphate and 1.0 g of lithium hydroxide, 5.0 g of diammonium hydrogen phosphate and 5.0 g of lithium hydroxide were used to form the surface modified composite oxide. Produced.

The thickness of the coating layer of Example 9 was 80 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer was 18 atom%, while the average concentration on the composite oxide side was 10 atom%. Electron diffraction images of the coating compound containing P and Al forming the coating layer were consistent with Li ₃ PO ₄ of ICDD No. 15-760 and γ-Al ₂ O ₃ of No. 10-425, respectively. As a result of converting the composite oxide after surface modification from ICP analysis, the weight ratios of P and Al compounds in the coating layer to the composite oxide were 5.0% and 1.5%, respectively.

  Table 3 shows the characteristics of the composite oxide prepared in Example 3.

  The exothermic peak was 275 ° C.

  In the same manner as in Example 1, a 18650 type battery was produced and the capacity retention rate was evaluated. The results are shown in Table 4.

  It can be seen that the battery using the positive electrode produced in Example 9 also has an energy density of 126 Ah / kg and exhibits high performance.

  In Example 10, a composite oxide was prepared in the same manner as in Example 1, and instead of using 3.0 g of aluminum nitrate and 1.0 g of lithium hydroxide as a raw material for surface treatment, 1.5 g of aluminum nitrate and 0 of lithium hydroxide were used. Using 0.5 g, instead of 1.0 g of diammonium hydrogen phosphate and 1.0 g of lithium hydroxide, 0.1 g of diammonium hydrogen phosphate and 0.1 g of lithium hydroxide were used to form the surface modified composite oxide. Produced.

The thickness of the coating layer of Example 10 was 10 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer was 8 atom%, while the average concentration on the composite oxide side was 0 atom%. Electron diffraction images of the coating compound containing P and Al forming the coating layer were consistent with Li ₃ PO ₄ of ICDD No. 15-760 and γ-Al ₂ O ₃ of No. 10-425, respectively. As a result of converting the composite oxide after surface modification from ICP analysis, the weight ratios of P and Al compounds in the coating layer to the composite oxide were 0.1% and 0.2%, respectively.

  Table 3 shows the characteristics of the composite oxide prepared in Example 3.

  The exothermic peak was 255 ° C.

  In the same manner as in Example 1, a 18650 type battery was produced and the capacity retention rate was evaluated. The results are shown in Table 4.

  It can be seen that the battery using the positive electrode manufactured in Example 10 also has an energy density of 131 Ah / kg and shows high performance.

  In Example 11, molybdenum oxide was used in addition to the material of Example 1 as a material for the composite oxide, and Li: Mn: Ni: Co: W was 1.04: 0.10: 0.42: 0.42: 0.02 was weighed to produce a composite oxide in the same manner as in Example 1. Then, instead of 1.0 g of diammonium hydrogen phosphate and 1.0 g of lithium hydroxide as the raw material for the surface treatment, 0.6 g of diammonium hydrogen phosphate and 0.6 g of lithium hydroxide were used for surface modification composite oxidation. The thing was produced.

The thickness of the coating layer of Example 11 was 20 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer was 10 atom%, while the average concentration on the composite oxide side was 5 atom%. Electron diffraction images of the coating compound containing P and Al forming the coating layer were consistent with Li ₃ PO ₄ of ICDD No. 15-760 and γ-Al ₂ O ₃ of No. 10-425, respectively. As a result of converting the composite oxide after the surface modification from ICP analysis, the weight ratios of P and Al compounds in the coating layer to the composite oxide were 0.6% and 0.4%, respectively.

  Table 3 shows the characteristics of the composite oxide prepared in Example 11.

  The exothermic peak was 250 ° C.

  In the same manner as in Example 1, a 18650 type battery was produced and the capacity retention rate was evaluated. The results are shown in Table 4.

  It can be seen that the battery using the positive electrode manufactured in Example 11 also has an energy density of 127 Ah / kg and exhibits high performance.

  In Example 12, titanium oxide is used in addition to the raw material of Example 1 as a raw material of the composite oxide, and Li: Mn: Ni: Co: Ti is 1.04: 0.60: 0.16: The composite oxide was prepared in the same manner as in Example 1 by weighing to 0.16: 0.04. Thereafter, a surface-modified composite oxide was produced in the same manner as in Example 1.

The thickness of the coating layer of Example 12 was 30 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer was 9 atom%, while the average concentration on the composite oxide side was 4 atom%. Electron diffraction images of the coating compound containing P and Al forming the coating layer were consistent with Li ₃ PO ₄ of ICDD No. 15-760 and γ-Al ₂ O ₃ of No. 10-425, respectively. As a result of converting the composite oxide after surface modification from ICP analysis, the weight ratios of P and Al compounds in the coating layer to the composite oxide were 1.0% and 0.4%, respectively.

  Table 3 shows the characteristics of the composite oxide prepared in Example 12.

  The exothermic peak was 265 ° C.

  In the same manner as in Example 1, a 18650 type battery was produced and the capacity retention rate was evaluated. The results are shown in Table 4.

  It can be seen that the battery using the positive electrode produced in Example 12 also has an energy density of 125 Ah / kg and exhibits high performance.

[Comparative Example 1]
Comparative Example 1 is a case where there is no oxide or fluoride containing a coating compound A (A is one or more elements selected from the group consisting of Mg, Al, Ti, Cu) forming the coating layer. These are compared with Examples 1-12.

  In Comparative Example 1, a composite oxide was produced in the same manner as in Example 1.

  Next, as a surface treatment for forming a coating layer, 100 g of the prepared composite oxide was added to 100 ml of ion-exchanged water in which 1.0 g of diammonium hydrogen phosphate and 1.0 g of lithium hydroxide were dissolved, and the mixture was treated at room temperature for 1 hour. The phosphoric acid compound was adhered to the surface of the composite oxide by stirring. The obtained powder was heat treated in the atmosphere at 650 ° C. for 5 hours to produce a surface-modified composite oxide.

The thickness of the coating layer of Comparative Example 1 was 10 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer was 12 atom%, while the average concentration on the composite oxide side was 11 atom%. The electron diffraction pattern of the coating compound containing P forming the coating layer was consistent with Li ₃ PO ₄ of ICDD No. 15-760. As a result of converting the composite oxide after the surface modification from the ICP analysis, the weight ratio of the P compound in the coating layer to the composite oxide was 1.0%.

  Table 5 shows the characteristics of the composite oxide produced in Comparative Example 1.

  The exothermic peak was 220 ° C. In Comparative Example 1, the exothermic peak was lowered in temperature compared with Examples 1 to 12 (exothermic peak 250-290 ° C. (see Tables 1 and 3)), and there was no metal (A) compound in the coating layer. For this reason, it is considered that the phosphoric acid compound is present non-uniformly and the effect of suppressing heat generation is reduced.

  In the same manner as in Example 1, a 18650 type battery was prepared and the capacity retention rate was evaluated. The results are shown in Table 6.

  From Table 6, the energy density is 130 Ah / kg in Comparative Example 1, whereas in Example 1, the energy density is 130 Ah / kg from Table 2, and in Examples 2-12, the energy density is from Table 4. 125-136 Ah / kg.

  Therefore, it was found that the batteries using the positive electrodes manufactured in Examples 1 to 12 maintained substantially the same energy density as compared with the battery using the positive electrode manufactured in Comparative Example 1.

[Comparative Example 2]
The comparative example 2 compares the case where there is no phosphoric acid compound which forms a coating layer with Examples 1-12.

  In Comparative Example 2, a composite oxide was produced in the same manner as in Example 1.

  Next, as a surface treatment for forming a coating layer, 100 g of the prepared composite oxide is added to 100 ml of ion-exchanged water in which 3.0 g of aluminum nitrate and 1.0 g of lithium hydroxide are dissolved, and the mixture is stirred at room temperature for 1 hour. An aluminum compound was adhered to the surface of the composite oxide. The obtained powder was heat treated in the atmosphere at 650 ° C. for 5 hours to produce a surface-modified composite oxide.

The thickness of the coating layer of Comparative Example 2 was 20 nm, and P was not present in the coating layer. Therefore, the average concentration on the surface layer side (electrolyte side) and the composite oxide side was 0 atom%. The electron diffraction image of the coating compound containing Al that forms the coating layer coincided with γ-Al ₂ O ₃ of ICDD No. 10-425. As a result of converting the composite oxide after the surface modification from ICP analysis, the weight ratio of the Al compound in the coating layer to the composite oxide was 0.4%.

  Table 5 shows the characteristics of the composite oxide produced in Comparative Example 2.

  The exothermic peak was 210 ° C. In Comparative Example 2, the exothermic peak was lowered in temperature compared with Examples 1 to 12 (exothermic peak 250-290 ° C. (see Table 1 and Table 3)), because there was no phosphate compound in the coating layer, This is probably because the effect of suppressing heat generation was greatly reduced.

  In the same manner as in Example 1, a 18650 type battery was prepared and the capacity retention rate was evaluated. The results are shown in Table 6.

  In Table 2, the energy density is 125 Ah / kg in Comparative Example 2, whereas in Example 1, the energy density is 130 Ah / kg from Table 2, and in Examples 2-12, the energy density is from Table 4. 125-136 Ah / kg.

  Therefore, it was found that the batteries using the positive electrodes manufactured in Examples 1 to 12 maintained substantially the same energy density as compared with the battery using the positive electrode manufactured in Comparative Example 2.

[Comparative Example 3]
Comparative Example 3 is a case where there is no concentration gradient between the surface layer side (electrolyte side) and the composite oxide side in the P coating layer of the phosphoric acid compound forming the coating layer. Compared to the case where there is a concentration gradient in (the concentration of P on the surface layer side (electrolyte side) is high and the concentration on the complex oxide side is low).

  In Comparative Example 3, a composite oxide was produced in the same manner as in Example 1.

  Next, as a surface treatment for forming a coating layer, 1.0 g of diammonium hydrogen phosphate and 1.0 g of lithium hydroxide are dissolved in 100 ml of ion-exchanged water in which 3.0 g of aluminum nitrate and 1.0 g of lithium hydroxide are dissolved. 100 ml of ion-exchanged water was added and stirred at room temperature for 1 hour. Next, 100 g of the prepared composite oxide was added and stirred at room temperature for 1 hour to attach a phosphate compound and an aluminum compound to the surface of the composite oxide. The obtained powder was heat treated in the atmosphere at 650 ° C. for 5 hours to produce a surface-modified composite oxide.

The thickness of the coating layer of Comparative Example 3 was 30 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer was 8 atom%, while the average concentration on the composite oxide side was 9 atom%. Electron diffraction images of the coating compound containing P and Al in the coating layer were consistent with IC3 No. 15-760 Li ₃ PO ₄ and No. 10-425 γ-Al ₂ O ₃ , respectively. As a result of converting the composite oxide after surface modification from ICP analysis, the weight ratios of P and Al compounds in the coating layer to the composite oxide were 1.0% and 0.4%, respectively.

  Table 5 shows the characteristics of the composite oxide produced in Comparative Example 3.

  The exothermic peak was 225 ° C. In Comparative Example 3, the exothermic peak was lowered in temperature compared with Examples 1 to 12 (exothermic peak 250-290 ° C. (see Tables 1 and 3)). The phosphate compound was uniformly present in the coating layer. However, it is considered that the effect of suppressing the heat generation was lowered because the electrolytic solution decomposition was not sufficiently suppressed on the surface layer side (electrolyte side).

  In the same manner as in Example 1, a 18650 type battery was prepared and the capacity retention rate was evaluated. The results are shown in Table 6.

  In Table 3, the energy density is 128 Ah / kg in Comparative Example 3, whereas in Example 1, the energy density is 130 Ah / kg from Table 2, and in Examples 2-12, the energy density is from Table 4. 125-136 Ah / kg.

  Therefore, it was found that the batteries using the positive electrodes manufactured in Examples 1 to 12 maintained substantially the same energy density as compared with the battery using the positive electrode manufactured in Comparative Example 3.

[Comparative Example 4]
In Comparative Example 4, the concentration on the surface layer side (electrolyte side) in the coating layer of the phosphoric acid compound forming the coating layer was lowered and the concentration on the composite oxide side was increased, and P in the coating layers of Examples 1 to 12 was increased. The concentration gradient was compared with the concentration gradient (in the example, the concentration on the surface layer side (electrolyte side) in the coating layer of P is high and the concentration on the complex oxide side is low).

  In Comparative Example 4, a composite oxide was produced in the same manner as in Example 1.

  Next, as a surface treatment for forming a coating layer, first, the composite oxide is added to 100 ml of ion-exchanged water in which 1.0 g of diammonium hydrogen phosphate and 1.0 g of lithium hydroxide are dissolved, and stirred at room temperature for 1 hour. Then, a phosphoric acid compound was attached to the surface of the composite oxide. Thereafter, 100 ml of ion-exchanged water in which 3.0 g of aluminum nitrate and 1.0 g of lithium hydroxide were dissolved was added and stirred again at room temperature for 1 hour. The obtained powder was heat treated in the atmosphere at 650 ° C. for 5 hours to produce a surface-modified composite oxide.

The thickness of the coating layer of Comparative Example 4 was 20 nm, and the average concentration on the surface layer side (electrolyte side) of P in the coating layer was 2 atom%, while the average concentration on the composite oxide side was 10 atom%. Electron diffraction images of the coating compound containing P and Al in the coating layer were consistent with IC3 No. 15-760 Li ₃ PO ₄ and No. 10-425 γ-Al ₂ O ₃ , respectively. As a result of converting the composite oxide after surface modification from ICP analysis, the weight ratios of P and Al compounds in the coating layer to the composite oxide were 1.0% and 0.4%, respectively.

  Table 5 shows the characteristics of the composite oxide prepared in Comparative Example 4.

  The exothermic peak was 220 ° C. In Comparative Example 4, the exothermic peak was lowered in temperature as compared with Examples 1 to 12 (exothermic peak 250-290 ° C. (see Tables 1 and 3)). This is presumably because the effect of suppressing heat generation was reduced because the electrolyte solution was not sufficiently suppressed on the surface layer side (electrolyte side).

  In the same manner as in Example 1, a 18650 type battery was prepared and the capacity retention rate was evaluated. The results are shown in Table 6.

  From Table 6, the energy density is 126 Ah / kg in Comparative Example 4, whereas in Example 1, the energy density is 130 Ah / kg from Table 2, and in Examples 2-12, the energy density is from Table 4. 125-136 Ah / kg.

  Therefore, it was found that the batteries using the positive electrodes manufactured in Examples 1 to 12 maintained substantially the same energy density as compared with the battery using the positive electrode manufactured in Comparative Example 4.

<Effect>
From the above, according to the present embodiment, the surface of the lithium manganese composite oxide having a layered structure has a phosphoric acid compound and one or more selected from the group consisting of A (A is Mg, Al, Ti, Cu). An oxide or fluoride containing), and P has an atomic concentration on the surface layer side (electrolyte side) in the coating layer that is higher than the atomic concentration on the lithium manganese composite oxide side. By using a positive electrode material for a lithium secondary battery that is characterized by being high, it is possible to provide a lithium secondary battery excellent in safety by suppressing heat generation when the temperature is raised in a charged state.

  The lithium secondary battery can be made highly safe particularly in a charged state.

<< Secondary battery system 10S equipped with lithium secondary battery 10 >>
Next, as Example 13, a secondary battery system 10S in which the lithium secondary battery 10 is mounted will be described.

  FIG. 6 shows an outline of a secondary battery system 10S on which the lithium secondary battery 10 produced in this embodiment is mounted.

  In the lithium secondary battery 10, for example, a plurality of 4 or more and 16 or less are connected in series to form a lithium secondary battery group 10 g. The secondary battery module 10M is configured by further including a plurality of such lithium secondary battery groups 10g. Of course, the number of the lithium secondary batteries 10 in the lithium secondary battery group 10g can be appropriately selected.

  The secondary battery module 10M includes a cell controller 11. The cell controller 11 is formed corresponding to the lithium secondary battery group 10 g and controls the lithium secondary battery 10. The cell controller 11 detects the voltage between the terminals of the lithium secondary battery 10, monitors the overcharge and overdischarge of the lithium secondary battery 10, and monitors the remaining capacity of the lithium secondary battery 10, thereby recharging the lithium secondary battery. 10 is managed.

  The battery controller 12 gives a signal to the cell controller 11 using, for example, the communication unit 14a, and obtains a signal from the cell controller 11 using, for example, the communication unit 14b. The battery controller 12 is connected to the outside via the signal line 13.

  The battery controller 12 performs power input / output management for the cell controller 11.

  For example, the battery controller 12 gives a signal to the input unit 111 of the first cell controller 11. Such a signal is continuously transmitted from the output unit 112 of the cell controller 11 to the input unit 111 of another cell controller 11. Such a signal is given to the battery controller 12 from the output part 112e of the last cell controller 11e.

  Thus, the battery controller 12 can monitor (monitor) the cell controller 11. The cell controller 11 and the battery controller 12 are appropriately configured using a computer, a circuit, etc., but are not limited thereto.

  Moreover, in FIG. 6, although the case where the lithium secondary battery 10 was connected in series was illustrated, the parallel connection which increases a capacity | capacitance may be sufficient, for example. Alternatively, the lithium secondary batteries 10 may be connected in a combination of series and parallel, and as long as the lithium secondary battery 10 is electrically connected, the connection mode is not limited and can be selected as appropriate.

DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Separator 4 Battery can 10 Lithium secondary battery (battery)
10M Secondary battery module 10S Secondary battery system 11 Cell controller (control device)
12 battery controller 111 input unit 112, 112e output unit

Japanese Patent No. 3244314 JP 2004-319129 A JP 2009-245917 A

Claims (12)

Composition formula LiMn _x M _1-x O ₂ (where 0.1 ≦ x ≦ 0.6, M is one or more elements selected from the group consisting of Li, Mg, Al, Ti, Co, Ni, Mo) In a positive electrode material for a lithium secondary battery having a lithium manganese composite oxide having a layered structure represented by:
A phosphoric acid compound and an oxide or fluoride containing A (A is one or more elements selected from the group consisting of Mg, Al, Ti, Cu) on the surface of the lithium manganese composite oxide. Having a coating layer comprising,
The positive electrode material for a lithium secondary battery, wherein an atomic concentration of phosphorus in the coating layer is higher on the surface layer side than on the lithium manganese composite oxide side. Composition formula _{LiMn x M 1-x O 2} ( where, 0.1 ≦ x ≦ 0.6, M is Li, Mg, Al, Ti, Co, Ni, Mo) one or more selected from the group consisting of In a positive electrode material for a lithium secondary battery having a lithium manganese composite oxide having a layered structure represented by
An oxide or fluoride containing a phosphoric acid compound and A (A is one or more elements selected from the group consisting of Mg, Al, Ti and Cu) on the surface of the lithium manganese composite oxide And a coating layer containing
The atomic concentration of phosphorus in the coating layer is such that the average value of the atomic concentration on the electrolyte solution (electrolyte) side from the central portion in the thickness direction of the coating layer is from the central portion in the thickness direction of the coating layer. A positive electrode material for a lithium secondary battery, characterized by being higher by 4 atom% or more than the average value of the atomic concentration on the side. 3. The positive electrode for a lithium secondary battery according to claim 1, wherein the phosphoric acid compound is at least one selected from the group consisting of Li ₃ PO ₄ , Li ₄ P ₂ O ₇ and LiPO _3. material.   The A in the oxide or fluoride containing A has an atomic concentration on the lithium manganese composite oxide side higher than an atomic concentration on the electrolyte side in the coating layer. Item 4. The positive electrode material for a lithium secondary battery according to any one of Items 3.   The content of the phosphoric acid compound is 0.1 wt% or more and 5.0 wt% or less with respect to 100 wt% of the lithium manganese composite oxide. The positive electrode material for lithium secondary batteries as described in any one.   The content of the oxide or fluoride containing M is 0.2 wt% or more and 1.5 wt% or less with respect to 100 wt% of the lithium manganese composite oxide. The positive electrode material for a lithium secondary battery according to any one of claims 5 to 6.   The thickness of the said coating layer is 2 nm or more and 80 nm or less, The positive electrode material for lithium secondary batteries as described in any one of Claims 1-6 characterized by the above-mentioned.   A lithium secondary battery comprising the positive electrode material for a lithium secondary battery according to any one of claims 1 to 7.   The lithium secondary battery according to claim 8, wherein when the positive electrode charged to 4.8 V is heated with the Li counter electrode, the main peak of heat generation is 230 ° C. or higher.   A plurality of electrically connected lithium secondary batteries according to claim 8 or claim 9, and a voltage between terminals of the plurality of lithium secondary batteries are detected, and the state of the plurality of lithium secondary batteries is controlled. A secondary battery module. A secondary battery module comprising: a plurality of electrically connected batteries; and a control device that manages and controls the state of the plurality of batteries, wherein the control device determines the inter-terminal voltage of the plurality of batteries. Each of the plurality of batteries comprises a laminated body having a positive electrode, a negative electrode, and an electrolyte in a battery can that forms an exterior, and the positive electrode has a composition formula LiMn _x M _1-x O ₂ (however, 0.1 ≦ x ≦ 0.6, wherein M is one or more elements selected from the group consisting of Li, Mg, Al, Ti, Co, Ni, and Mo). A coating layer containing a phosphate compound and an oxide or fluoride containing A (A is one or more elements selected from the group consisting of Mg, Al, Ti, and Cu) on the surface of the composite oxide Having phosphorus in the coating layer, the atomic concentration on the surface layer side Is higher than the lithium manganese composite oxide side.   The phosphorus of the phosphoric acid compound has an atomic concentration on the surface layer side (electrolyte side) higher than an atomic concentration on the lithium manganese composite oxide side in the coating layer. Next battery module.

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